Journal of Electroanalytical Chemistry 464 (1999) 48 53

Modied electrodes based on mixed bentonite vanadium(V) oxide xerogels

Fauze J. Anaissi a, Gregoire J.-F. Demets a, Henrique E. Toma a*, Antonio C.V. Coelho b
a

Instituto de Qu mica, Uni6ersidade de Sa o Paulo, Caixa Postal 26077 CEP 05599 -970, Sa o Paulo SP, Brazil b Departamento de Engenharia Qu mica, Escola Polite cnica, Uni6ersidade de Sa o Paulo, Brazil Received 22 June 1998; received in revised form 17 November 1998

Abstract A novel type of composite xerogel can be obtained by the combination of polyvanadic acid and bentonite clay, displaying a characteristic green colour, associated with the presence of vanadium(IV) sites and intervalence-transfer bands in the near-infrared region. The slow evaporation of the xerogel suspensions leads to lamellar solids containing vanadium(V) oxide and silicate layers. In contrast to the vanadium-oxide lms, the composite xerogels are not soluble in water, showing a good electrochemical response when applied onto electrode surfaces. Enhanced electrochemical signals are observed in the presence of electroactive species such as the hexaammineruthenium(II) complexes, reecting their intercalation into the interlamellar space. 1999 Elsevier Science S.A. All rights reserved. Keywords: Bentonite; Vanadium oxide; Lamellar composite; Modied electrodes < /kwdg*

1. Introduction An interesting aspect of vanadium(V)-oxide xerogels is their conversion into a lamellar type of solid by slow evaporation at room temperature. This solid is made up of layers of polyvanadate ribbons linked by water molecules and exhibits very interesting electronic and electrochemical properties associated with the occurrence of mixed valence interactions and ionic transport. A number of applications has been reported, particularly in batteries, catalysis, nanocomposites and advanced materials [1 24]. However, for electrochemical purposes, the usefulness of the vanadium(V)-oxide lms is restricted to organic solvents, because of their appreciable solubility in aqueous solutions. From the structural point of view, the hydrated vanadium(V) oxides resemble the montmorillonite

* Corresponding author. Tel.: + 55-11-8183887; fax: + 55-118155579.

clays, such as bentonite. This is a typical lamellar solid containing a variable amount of water and exchange . The able cations in the interlayer spacing of ca. 15 A inclusion of electroactive species into the bentonite lms has been exploited in modied electrodes [2529]. In this case, a polymer coating is required, in order to prevent the gradual loss of the bentonite particles from the electrode. The idea of combining vanadium(V)-oxide and montmorillonite clays was inspired by their similar structural properties. Our initial attempts revealed that a gelatinous material was formed by treating aqueous bentonite suspensions with polyvanadic acid. This peculiar material with the appearance of green algae immediately attracted our attention. Considering the current electroanalytical interest in this type of material [3032] we started investigating the bentonite vanadium(V)-oxide composites, here denoted BV, as electrode modiers, focusing on their structural characterization and evaluation of relevant thermal, spectroscopic and electrochemical properties.

0022-0728/99/$ - see front matter 1999 Elsevier Science S.A. All rights reserved. PII: S 0 0 2 2 - 0 7 2 8 ( 9 8 ) 0 0 4 6 5 - 3

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2. Experimental Polyvanadic acid solutions (0.1 mol dm 1) employed in the preparation of the vanadium(V) oxide xerogels were generated from sodium metavanadate (Alpha), after passing through a Dowex 50W-X4 ion exchange resin, in the H + form (Baker) as reported in the literature [18,19]. A stock, colloidal suspension of bentonite (Aldrich) was prepared by stirring, for several days, 5 g of the nely ground dry powder into 250 ml of water. Before each experiment, the mixture was stirred vigorously and allowed to rest for at least 2 h. The amount of bentonite in the colloidal suspension was calculated as 1.64%, from the mass of the residue obtained after drying at 110C. In a typical preparation, the bentonite vanadium(V) oxide xerogels were obtained by adding 10 ml polyvanadic acid solution (containing 1 mmol V) to 20 ml of the bentonite suspension (containing approximately 1.0 mmol Al2O3Si4O10H2O), under vigorous stirring, and allowed to rest for 24 h. After this, a green occulent solid appeared. This gelatinous suspension was decanted carefully in order to remove the colloidal bentonite particles and the excess of the polyvanadic acid, and then dispersed in water. The procedure was repeated several times, until colorless and clear washings were obtained. Finally, the green solid was collected on a lter, washed with water and stored in a closed bottle. The yield, in this case, was around 10%. The proposed composition was expressed in terms of bentonite and vanadium-oxide, assuming the approximate stoichiometric formulae Al2O3Si4O10H2O (MW = 360 g mol 1) and V2O5 (MW = 182 g mol 1), respectively. Diffuse reectance electronic spectra were recorded on a Guided Wave model 260 spectrophotometer, using ber-optics Wand probes. Vanadium(V) analyses were carried out spectrophotometrically using the vanadatehydrogen peroxide method, as described in the literature [33]. X-ray powder diffraction measurements were carried out using a Phillips XPERT MPD diffractometer, equipped with a copper tube (Cu Kh ; 40 kV, 40 mA, step rate = 0.02 s 1) and monochromator. TG and DTG measurements were carried out using a Shimadzu TGA-50 thermobalance at a heating rate of 10C min 1, under a nitrogen atmosphere. Cyclic voltammetry was carried out on a Princeton Applied Research model 283 potentiostat attached to a PC compatible computer, using an Ag  AgCl  KClsat reference electrode and a Pt disk (0.025 cm2) working electrode, as reported previously [34 36]. Optical photomicrography (330 magnication) was carried out on a Photo-optical innity microscope equipped with a Panasonic ccd color camera attached to a PC compatible computer. Electron microscopy was carried out on a Leika model Stereoscan 440 electron scanning microscope equipped with elemental uorescence analy-

sis. FTIR vibrational spectra were recorded on a Bomem spectrophotometer.

3. Results and discussion The reaction of aqueous polyvanadic acid (orange) and colloidal bentonite (white-gray) under vigorous stirring, yields an unusual green occulent material, resembling algae in suspension. The unreacted polyvanadic acid remains dissolved in the yellowish solutions containing the excess of colloidal bentonite, allowing the purication of the oating green product by decantation and successive washings with water. No similar product is observed by stirring polyvanadic acid or bentonite species separately, under a wide range of experimental conditions (pH, temperature and reaction time). Therefore, the green solid should result from the interaction of polyvanadic acid and bentonite. In fact, by varying the relative amounts of polyvanadic acid and bentonite, a number of compositions can be obtained for the solids. In this work, a typical sample obtained by starting from nearly stoichiometric (1:1) amounts of the reagents (see Section 2) was employed for the purposes of investigating the electrochemical properties of this type of material. However, a systematic work is in progress, in order to improve the understanding of the novel mixed composites. The composition of the isolated solids was estimated based on vanadium(V) analyses, thermogravimetry and on the mass of the insoluble silicate residue obtained from acid digestion. The several repetitive analyses using different samples exhibited an appreciable scattering (1020%) as a consequence of the rather empirical synthetic and analytical procedures, supporting however, the approximate composition Al2O34(SiO2) x (V2O5)y (H2O), where x = 2.73.5 and y = 2.63.5. This composition departs from the 1:1 (bentonite:vanadium) stoichiometry employed in the synthesis, suggesting the formation of a new composite material involving the two species, rather than a simple mixture of the starting materials. The hypothesis of a mixture can be ruled out since the vanadium oxide xerogel is soluble in water, and in this case it would be removed after the successive washings. On the other hand, bentonite forms a colloidal suspension which can be separated readily from the occulent material. Therefore, only a minor fraction would remain included in the occulent gel, after the washing process. The X-ray diffraction pattern for this solid is typical of a bidimensional, layered structure, and is comparable with those observed for hydrated vanadium(V)-oxide and bentonite, as shown in Fig. 1. The basal distance calculated from the 001 diffraction peak was . This value is intermediate between the distances 12.8 A observed for the starting materials, of 10.8 and 15.2 A

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reecting the inuence of the structural characteristics of the two species in the composite. It should be noted that the 001 peaks in the starting materials are well separated, and the 001 peak of the mixed BV composite is narrow and well dened, ruling out any possible interpretation in terms of a mixture of the starting materials. By using the modied Scherrer equation [37] it was possible to estimate the average dimensions of the microscopic domains containing the oriented layers, , respectively, for the BV comas 250, 58 and 150 A posite, and the starting bentonite and vanadium-oxide materials. The TG and DTG plots for the BV and starting materials are shown in Fig. 2, for comparison purposes. The weight loss occurs essentially in the range of 30 400C, and is associated with the removal of water from the solids. In the case of bentonite, the total mass loss corresponds to ca. 1.3 molecules of water which are released below 120C. For the hydrated vanadium(V) oxide, three dehydration steps have been identied (Fig. 2(C)). The rst step proceeds up to 120C, corresponding to the release of the weakly bound water molecules from the surface and the interlamellar space. The second step proceeds with a gradual mass loss in the range of 120270C, corresponding to the removal of 0.3 H2O, without disrupting the lamellar structure. The third step is characterized by a rapid loss of ca. 0.2 H2O, around 300C, leading to pronounced structural changes. In the case of the BV solids, the thermal

Fig. 2. TG and DTG plots for bentonite (A), BV composite (B) and hydrated vanadium(V) pentoxide (C) under a constant ow of nitrogen.

Fig. 1. X-ray powder diffractograms for the bentonite, hydrated vanadium(V)-pentoxide and the mixed BV composite (CuKh u = ). 1.5418 A

behavior (Fig. 2(B)) is consistent with the release of 2.5 weakly bound water molecules below 120C, followed by a second step around 180C involving 0.6 H2O strongly bound in the interlayer space, and a more gradual process up to 400C corresponding to 0.4 H2O. The BV composite employed in the preparation of lms was kept suspended in pure water, and stored in this way for several weeks with no evidence of decomposition. The application of one small drop of this suspension onto the electrode surfaces yielded greenish lms, after solvent evaporation at room temperature. The surface characteristics of the BV modied electrodes were examined in a routine way, by means of reectance optical microscopy, revealing good homogeneity and coverage. The typical morphology of the green composite lm can be seen in the scanning electron microscopy picture shown in Fig. 3. Elemental analysis using a uorescence X-ray probe indicated the presence of the V, Al and Si elements (Fig. 3). The relative peak intensities varied less than 10% for the several regions of the sample probed by the analytical detector, showing the presence of the three elements in a consistent way, and ruling out the hypothesis of a mixture of bentonite and vanadium oxide. On the other hand, the observed morphology

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differs from the ribbon-like aspect of the pure V2O5 xerogels, and the platelets shape of bentonite. The FTIR spectrum of hydrated vanadium(V)-oxide lms consists of a strong band at 1010 cm 1 ascribed to the V O stretching vibration of the vanadyl group, and strong peaks at 760, 522 and 470 cm 1 associated with in-plane and out-out-of plane V O V vibrational modes involving the vanadium-oxide bridges [38]. Bentonite exhibits strong characteristic peaks at 1045 cm 1 associated with SiO stretching vibrations, and at 512 and 466 cm 1 arising from vibrational modes of the Si O Al bridges [39]. In the case of the BV composites the expected V O and Si O peaks at 1010 1045 cm 1 become relatively weak, while the V O V and Si O Al vibrational peaks appear superimposed at 766, 522 and 466 cm 1. However, a new, broad, strong peak can be detected at 835 cm 1, in a valley region of the bentonite and vanadium(V)-oxide absorption proles. The rise of the 835 cm 1 peak, and the decay of the V O and SiO peaks at 1010 1045 cm 1 observed in the starting materials, suggests the formation of V O Si bonds in the mixed composite. The existence of a new composite material is also evident from the observed changes of solubility. In contrast to the vanadium-oxide lms which are soluble in water, and the bentonite lms which are poorly adherent and dispersed easily in the solvent, the mixed BV lms are strongly adherent to the electrode surface and exhibit a remarkable stability in aqueous solutions. The electrochemical behavior of a typical BV modied (platinum) electrode in aqueous 0.1 mol dm 3 LiClO4 is shown in Fig. 4(A). By starting at 300 mV, the rst negative scan led to a large current response which reached a maximum around 100 mV versus (Ag  AgCl). This response is probably associated with the electrolyte migration and the reorganization of the redox sites in the composite. After the rst scan the

Fig. 4. (A) Cyclic voltammogram of a BV modied platinum electrode immersed in D2O containing 0.10 mol dm 3 LiClO4, scan rate = 10 mV s 1; and (B) the corresponding absorption spectra recorded in situ by applying 300 or 400 mV.

Fig. 3. BV lm morphology and elemental analysis probed with an electron scanning microscope equipped with X-ray uorescence detection.

electrochemical response reaches a stationary condition, as one can see in Fig. 4(A). The in situ electronic spectrum of the BV modied electrode is illustrated in Fig. 4(B). The spectrum was recorded in D2O solutions containing 0.1 mol dm 3 LiClO4, in order to minimize the interference of the absorption band of water in the near infrared region. As one can see in the gure, the spectrum is dominated by a strong, broad absorption band which starts in the visible and reaches a maximum in the near-infrared region, around 1400 nm. This band is typical of VIV VV intervalence transitions in polyvanadate lms, and its strong intensity is coherent with a high concentration of mixed-valence sites or electronic vacancies in the composite. In addition, one can see the absorption tail below 400 nm, associated with the charge-transfer bands in the oxo-vanadium(V) species. At more positive potentials (e.g. 300 mV) a less intense absorption appears at 500 nm as a shoulder at the beginning of the intervalence transfer band. This band may be due to ligand eld transitions in the VIV sites as well as to the Fe(II)/(III) impurities in the bentonite layers. It is inter-

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esting to note that the initial amount of VIV sites is very high, and that the electrochemical cycling produces only a small change in the electronic bands. Apparently, after a few cycles, the stationary voltammograms and spectroelectrochemical changes approach the behavior of typically metallic electrodes. In all the cases, the BV lms remained intact during the experiments, with no evidence of loss or dissolution from the electrode surface. The conducting properties of the BV modied electrodes were also investigated in the presence of electroactive species, such as the hexaammineruthenium(III)/(II) ions. This complex has been employed previously by Oyama et al. [30], to test the performance of Naon coated bentonite modied electrodes, and was considered particularly suitable for comparison purposes. As one can see in Fig. 5(A), after the rst negative scan, the modied electrode exhibited the typical response of a metallic electrode, showing a quasi-reversible response for the external [Ru(NH3)6]3 + /2 ions during the initial cycles. After the fth cycle, a consistent current enhancement became discernible in

the voltammograms as a function of the many successive scans. This type of behavior departed from the conventional behavior of a solid electrode, suggesting the occurrence of electrochemical intercalation of the hexaammineruthenium(III) complexes into the BV lm. In order to test for this hypothesis, after 20 successive cycles, the electrode was removed from the solution containing the electroactive species, washed with water and reintroduced into the electrochemical cell containing solely the electrolyte solution. In accord with our expectation, the electrochemical response (Fig. 5(B)) indicated the presence of the intercalated complex, reproducing the previous results, in spite of the absence of the electroactive species in solution. In addition, the observed peak currents exhibited a linear increase with the scan rates (Fig. 5(B) inset) as expected for the intercalation of the hexaaminruthenium(III) ions into the BV lms.

4. Conclusions The mixed bentonite-vanadium oxide composites constitute a very attractive electrochemical material, combining the good conductivity of the vanadium(V)oxide lms with the ion exchange and intercation properties of the lamellar clays. The inuence of the vanadium-oxide layers is readily apparent in the colour, spectroelectrochemical and conducting properties of the BV composite, while the electrochemical intercalation behavior is similar to those reported previously for Naon coated bentonite modied electrodes [30]. However, because of its low solubility in water, the use of the BV composite does not require specic polymer coatings, allowing one to work under natural conditions, and leading to an enhancement of the electrochemical response by at least four orders of magnitude, due to the pre-concentration effect. In addition, the lamellar structure of the BV composites supports a number of applications in electrochemistry and intercalation chemistry. Along this line, a detailed investigation of BV and its intercalated composites is being pursued in this laboratory.

Acknowledgements The authors gratefully acknowledge the nancial support from PADCT, FAPESP and CNPq.
Fig. 5. (A) Repetitive cyclic voltammograms of a BV modied platinum electrode immersed in aqueous solution containing 3.0 mmol dm 3 [Ru(NH3)6]3 + and 0.10 mol dm 3 LiClO4; (B) Cyclic voltammograms of the BV modied electrode removed after the 20th cycle, after washing with water and immersing in pure electrolyte solution (Inset: cathodic peak currents versus scan rate).

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